Synthetic oils

ABSTRACT

THE PRESENT INVENTION RELATES TO SYNTHETIC OILS WHICH ARE TERTIARY-ALKYLATED BENZENE AND -NAPHTHALENE, WHEREIN THE TERTIARY ALKYL SUBSTITUENTS CONTAIN FROM 7 TO 44, PREFERABLY AN AVERAGE OF FROM 14 TO 44 CARBON ATOMS. THE COMPOSITIONS HAVE UTILITY AS HYDRAULIC OILS, AS LUBRICANTS, AND IN THE FORMULATION OF GREASES. THE TERTIARY ALKYL-BENZENES AND -NAPHTHALENES HAVE HIGHER BOILING POINTS AND LOWER VISCOSITIES THAN THE NATURAL PETROLEUM OILS OF THE SAME AVERAGE NUMBER OF TOTAL CARBON ATOMS, THEREBY PROVIDING A SUPERIOR PRODUCT WHERE LOW VOLATILITY AND HIGH FLASH POINT AT A GIVEN VISCOSITY ARE REQUIRED. THE SUBSTANTIAL ABSENCE OF A HYDROGEN ATOM ON THE CARBON ALPHA TO THE BENZENE RING MAKES THE COMPOSITIONS OF THE PRESENT INVENTION MUCH SUPERIOR IN OXIDATION AND THERMAL STABILITY AS COMPARED TO THE PRIMARY AND SECONDARY ALKYL BENZENES AND NATURAL PETROLEUM OILS WHICH ARE AVAILABLE.

United States Patent 3,766,285 SYNTHETIC OILS Jesse K. Boggs, Houston,Tex., and Arthur W. Langer, Jr., Watchung, NJ., assignors to EssoResearch and Engineering Company No Drawing. Filed Dec. 28, 1970, Ser.No. 102,173 Int. Cl. C07c /04 U.S. Cl. 260-668 R 6 Claims ABSTRACT OFTHE DISCLOSURE The present invention relates to synthetic oils which aretertiary-alkylated benzene and -naphthalene, wherein the tertiary alkylsubstituents contain from 7 to 44, preferably an average of from 14 to44 carbon atoms. The compositions have utility as hydraulic oils, aslubricants, and in the formulation of greases.

The tertiary alkyl-benzenes and -naphthalenes have higher boiling pointsand lower viscosities than the natural petroleum oils of the sameaverage number of total carbon atoms, thereby providing a superiorproduct where low volatility and high flash point at a given viscosityare required. The substantial absence of a hydrogen atom on the carbonalpha to the benzene ring makes the compositions of the presentinvention much superior in oxidation and thermal stability as comparedto the primary and secondary alkyl benzenes and natural petroleum oilswhich are available.

The present invention relates to synthetic oils for use in a number ofservices, such as hydraulic oils, lubricating oil base stocks, basestocks for grease formulation, etc. The compounds have a higher boilingrange and higher flash point than oils of the same viscosity which arefrom conventional processing of petroleum. Further, the compounds of thepresent invention are much more resistive to oxidation and thermaldegradation than primary and secondary-alkylated aromatics since they donot possess significant amounts of benzylic hydrogens (a hydrogen atomon the alpha carbon to the benzene ring). They are also superior toconventional petroleum oils with respect to these characteristics.

The compounds of the present invention are predominantly tertiaryalkylated-benzene and -naphthalene. Benzene may be either mono ordisubstituted, whereas naphthalene will be mono or higher substituted.

The composition of the present invention consists essentially of one ormore compounds which correspond to the structural formula:

wherein R R and R are alkyl groups,

R, is hydrogen or a t-alkyl group,

A is benzene or naphthalene, and the total number of carbon atoms in allsubstituents attached to A is from 7 The composition contains less thanabout 40 weight percent, preferably less than about 15 weight percent,of compounds possessing benzylic hydrogen atoms. Where A is naphthalene,R is hydrogen, usually.

The compositions may, if desired, be hydrogenated to saturate thearomatic nucleus. In such case, A will be a naphthenic radical.

The total number of carbon atoms in alkyl substituents, whether in asinglesubstituent or in two substituents, will range from 7 to 44,preferably from 14 to 44. The dialkyl- 3 ,766,285 Patented Oct. 16, 1973"ice benzenes, because of their higher viscosity, are particularlysuitable for grease formulations, whereas the monoalkylbenzenes areparticularly useful in lubricating oil and hydraulic oil service;however, t-alkyl benzenes may be used as grease base oils where thet-alkyl group contains enough carbon atoms (e.g., 27 carbon atoms).Exemplary corn pounds for various uses are C H t-alkyl benzene (hydraulic oil for low temperature service), C H t-alkyl benzene (lubeoil), and C27H55 t-alkyl benzene (grease base oil). In each of the aboveexamples, the carbon and hydrogen amounts refer only to the t-alkylsubstituent and do not include those in the benzene nucleus. The numbersrepresent the average carbon and hydrogen content of the substituents.

The compounds of the present invention are prepard by the methoddisclosed and claimed in copending application Ser. No. 101,921,entitled Selective Tertiary Alkylation of Aromatic Hydrocarbons by JesseK. Boggs, filed on an even date herewith, the disclosure of which isincorporated into this application by reference. In that copendingapplication, it is disclosed that the tertiary alkylation of aromatichydrocarbons, utilizing bulky tertiary alkyl substituents, can beaccomplished with selectivity and high yield only if a tertiary alkylhalide is used as the al-kylating agent and only if the evolved hydrogenhalide is rapidly removed from the reaction zone, e.g., by operatingunder substantially reduced pressure.

As will be hereinafter more fully spelled out, a large number ofsynthetic oils have been prepared by the process of the copendingapplication. These compositions are superior in oxidation resistance andin the resistance to thermal degradation.

GENERAL The compositions of the present invention are useful aslubricants (oils and greases) and as hydraulic oils. The particularcompound or mixture of compounds will be chosen to meet the needs of thespecific use to which the product will be put. For lubrication service,the average number of carbon atoms in substituent groups will be from 14to 44. When it is desired to obtain the lowest viscosity for a givenboiling range, benzene will be the nucleus. Generally, the lower tomiddle range viscosity (i.e., from 2 to 6 cs. at 210 F.) alkyl benzeneswill be used as a lube oil base stock, while high viscosity (e.g.,greater than 6 cs. at 210 F.) will be used as grease bases. Theviscosity index (VI) improves as one R group of the t-alkyl substituentbecomes longer, but the pour point also increases. For some uses (e.g.,as a textile lubricant) the VI and pour point are not critical-the lowvolatility for a given viscosity exhibited by these compounds is thedesideratum. For other uses, such as automotive engine lubricants, theVI and pour point are important and are balanced off by selecting aproper tertiary-alkylated compound (or, usually, mixture of compounds)prepared in accordance with the present invention. The pour point isreduced by using a mixture of compounds rather than a single, purecompound.

The compounds of the present invention exhibit a lower volatility for agiven viscosity and a better balance of viscosity and boiling point fora given number of carbon atoms as compared to prior art lubricantcompositions.

OLEFINS SUITABLE AS HALIDE SOURCES The t-alkyl benzenes and naphthalenesof the present invention are obtained by alkylating the aromatic nucleuswith a suitable t-alkyl halide. A preferred source of t-alkyl halides isthe product obtained by hydrohalogenation of the mixed 2-alkyl-1-alkenesproduced by dimerization of a-olefins of differing carbon numbers. Theresulting mixture of t-alkyl halides provides alkylated aromatichydrocarbon mixtures of, superior viscosity, viscosity index and pourpoint characteristics. Where a single wolefin is used as a dimerizationfeedstock, the resultant olefin presence of a suitable catalyst, such asdiisobutyl aluminum hydride [Al(isobuty1). I-I]. For example, from about0.5 to 5.0 weight percent of diisobutyl aluminum hydride in thea-olefins forms the reaction mixture at elevated temperatures (e.g., 250F. to 450 F.) and;

modest pressure (e.g., 0 to 100 p.s.i.g.) for 1 to 30 hours. Thereactionrproceeds as follows:

when heated during distillation and/or in an acidsystem (A1 0 or HCl),the olefin product isomerizes:

In either case, the product ,upon hydrochlorination would be the same, 7

the tertiary chloride alkylating agent.

For convenience in discussing the structures of the tertiary halides,the number of carbon atoms in the K group around the central carbon atomare referenced by the corresponding numerals as shown below: GeneralStructure 7 Example 7 Ba CH3 lh--R; CtIIn-C-CrrHts R, R2, R3 structure4-1-12 structure ably balancing theratio of low-boiling solvent tobenzene,v

and the reaction temperature and pressure. A. Friedel- Crafts catalyst(preferably FeC1 is used to promote the alkylation reaction. The HClwhich is evolved is. rapidly held within the desired range and thereaction products withdrawn in the vapor phase to the controlled vacuum.line. The reaction products (mainly HCl) and volatilized liquid(aromatic hydrocarbon or cosolvent) were removed at a rate sufiicient tomaintainthe hydrogen halideconcentration in the liquid phase at theindicated level. A stripping period at even further reduced pressure wasusually employed at the end' of the vacuum runs. In some runs, whereatmospheric pressure was employed, the vacuum was not drawn and thereflux condenser was allowed to reach equilibrium with the. outside air.

Example 1 Alkylation of benzene with 3-chloro 3 ethylpentane (22-2)using conventional alkylating conditions. This example shows that theuse of atmospheric pressure is unsuitable with A1Cl leading to theformation. of nontertiary alkyl product, even when using a C t-alkylchloride.

A S-Iiter'flask in a water'bath was used for this example, and it wasequipped with five outlets for a. calibrated. dropping funnel, athermometer, an inlet for liquid butane,

' a vent tube, and a magnetic stirrer.

The pot was charged with 585 g. of prechilled dry benzene, 13 g. ofanhydrous AlCl and 598 g. of butane. The dropping funnel was chargedwith 135 g. of 3-c-hloro-3- ethylpentane and 585 g. of dry benzene. Thecontents, of thedropping funnel were added over a period of 1.6 hoursand the temperature in the flask allowed. to rise from an initial 7 C.to about 28.5 C. The pressure was 760 mm. Hg. After completion of thereaction, the product was water washed and the butane and benzenestripped. from the reaction product. Gas chromatographic and NMRanalyses were then carried out to determine that the yield was 83% ofalkylate but that over 99% of the product was nontertiaryin structure. 7

Example 2 Alkylation of benzene with 2-chloro-2-methylhexadecane l-1-14)chloride using ferric chloride as a catalyst. The flask was charged with1.6 g. of ferric chloride (anhydrous) and 24 g. of dry benzene. Thedropping tunnel was charged with *24 g. of dry benzene and 28 g. of the(l114) chloride. The flask contentswerechilled to about 5 C., pressureadjusted at 60-75 mm. Hg and the. contents of the dropping funnel addedover a period of 20 minutes. The temperature was held at 3-'-7 C; andthe reaction proceeded very rapidly ,assho'wn by vigorous boiling andthe evolution of HCl gas through the bub- V bler. After the chloride wasadded, 5 g. of additional ben zene' were added and conditions maintainedfor a further 7 40minutes. After this time, the pressure was reduced toremoved from the reaction zone to minimize the formai tion ofundesirable secondary alkyl isomers.

EXAMPLES In order to illustrate the production of thhe compositions ofthe present invention, the following examples are given. In most ofthese examples,.the reaction was carried out in a three-neck, 250 m1.flask, connected to a reflux about 20-30 mm. Hg' and held for 15minutes. to strip.

the reaction liquid phase of remaining volatile components. The contentsthen were poured over an ice-salt mixtureto terminate the reaction.After working up the product by three (aqueous) saturated NaCl washes(100 ml. each) and filtering, the benzene was removed on arotatingevaporator. The yield of stripped product was 29.4

condenser and bubbler and, also to a source of controlled vacuum, with adropping funnel being provided for the introduction of a liquid feed.The reaction flask was provided with .a thermometer, a magnetic stirrerand a cooling bath. In the examples, the Friedel-Crafts catalyst in thearomatichydrocarbon was charged to the flask, while 7 for the solubil tyof HCl in benzene. At atmospheric pres sure and the same temperature,the calculated HCl concentration would have been 0.0529 mol fraction. 7

Example 3 Alkylation of benzene with 2-chloro-2i-methylhexadecane1-1-14) using AlCl as a catalyst. The flask was charged with 24 g.'ofdry benzene and 1.3 g. of anhydrous aluminum chloride. The droppingfunnel was charged 7' with 24 g. of dry benzene and 28 g. of (1-1-14)chloride. The flask contents were chilled to 6-10 C., the pressureadjusted to 50-60 mm. Hg absolute, and the contents of the droppingfunnel added over a period of 21 minutes. The reaction was held anadditional 55 minutes at a pressure of 50-60 mm. Then full house vacuum(20-30 mm.) was applied and held for an additional 15 minutes. Theproduct was worked up as in Example 1 and 26.1 g. of yield wereobtained. The maximum HCl concentration during the reaction wascalculated at 0.00450 mol fraction. Under the same conditions at 760mm., the concentration would have been 0.0488 mol fraction.

The product was examined by NMR and found to contain only 16%nontertiary alkylbenzenes and 84% desired tertiary alkylbenzene.

Example 3 illustrates that aluminum chloride can be used as a catalystunder our preferred conditions, with only .a .small amount of undesiableisomerization occuri Example 4 This example shows that with FeCl benzenecannot be successfully alkylated with the C (1-1-14) olefin rather thanthe (1-1-14) chloride. The flask was charged with 24 g. of dry benzeneand 1.6 g. of FeCl (anhydrous). The dropping funnel was charged with 24g. of benzene and 24 g. of the (l-1-14) branched olefin. The flask andits contents were held with stirring at atmospheric pressure andC.'while the benzene/olefin mixture in the dropping funnel was addedover a period of 20 minutes. The ice bath was removed and the flaskwarmed to room temperature (25 C.) for an additional hour. Onemilliliter samples were taken at 15, 30 and 45 minute intervals afterthe start and at the end of the reaction. After 1 hour and 20 minutes,the reaction mixture was poured over an ice-salt mixture, separated andwashed three times with 100 ml. of a saturated NaCl aqueous solution. Itwas paper filtered and benzene removed on the rotating evaporator. Ayield of 21.6 g. was obtained, but gas chromatograph data showed noalkylation product in any of the samples.

Example 4 illustrates that with FeCl tertiary alkylation with the olefincannot be c-arried out directly, but that the use of the alkyl halide isnecessary.

Example 5 (dialkylation) This example shows the alkylation of benzenewith two tertiary alkyl groups. The procedure of Example 5 was similarto that of Example 1, but was carried out in two steps and in equipmentwhich was larger than that used in Example 1. In step 1, 1560 g. of drybenzene and 24.3

previously described. The product was distilled to recover the tertiaryamylbenzene overhead (yield 387 g.) and this was used as the charge forthe second step. Under the conditions employed, the maximum HClconcentration was about 0.0277 mol fraction as compared to 0.0515 molfraction which would have been present at 760 mm. About 90% of the feedchloride was converted to give a mixture of about 2.6 mols of crudemonotertiary amylbenzene and 0.14 mol of crude ditertiary amylbenzene.

119 g. of the tertiary amylbenzene from step 1 and 5.7 g. of FeCl(anhydrous) were charged to the flask. The dropping funnel was chargedwith 176 g. of 2-chloro-2- methyltetradecane (1-1-12). The alkylchloride was added over a period of 1 hour to the flask which wasmaintained under a temperature of 0 to 5 C. and a pressure of 40 mm. Hgabsolute. It was held for an additional hour underthose conditions andthe temperature then raised to 20 C. for 15 minutes and the pressurethereafter reduced to 15 mm. Hg for an additional 20 minutes. Theproduct was worked up and examined to determine the nature of theproduct. Only about 15% of the product contained a hydrogen atom alphato the ring.

Although some isomerization did take place with the heavier fractions,the alkyl attachments remained predominantly tertiary. This is true evenin the bottoms fraction recovered from step 1 where the maximumnontertiary attachment was seen to be 15 by NMR examination. Thecalculated maximum HCl concentration in the second step was 0.00349 molfraction as compared to 0.0585 for the same alkylation if conducted at760 mm. Hg pressure.

The di-t-alkyl product was of the formula:

This example shows the production of a dialkyl benzene having nohydrogen atoms alpha to the ring.

Examples 6 through 14 Following the same general procedure as abovedescribed, a number of other runs were made with different alkylatingagents and with different Friedel-Crafts catalysts. The results of theseruns are tabulated below in Table I, wherein the alkylating agent isidentified by the number of carbon atoms in R R and R Table Iillustrates that tertiary alkylation of benzene has been accomplished ingood selectivity so that the product is the improved synthetic oil ofthe present ing. of FeCl (anhydrous) were charged to the flask whilevention.

- TABLE I.ALKYLATION 0 BENZENE WITH TERTIARY AKLYL CHLORIDES Conver-Press., sion Selec- Example Alkyl mm. Max. H01 Reaction Temp., motivity, number agent Catalyst Hg mol tract. time, hrs. 0 percent percentFeCla 28 0.00142 1. 7 0 84. 8 95 FeCls 300 0. 01622 3. 0 12-22 92. 886-96 FeCh 300 0. 01820 4. 0 6-15 95. 8 91 FeOla 40 0.00300 2. 3 6 87 95eGh -75 0. 00287 1. 9 6-20 90 FeCls 300 0. 01625 4. 0 12 95 80-96(AlClQ-(FeCla); 39 0. 00221 0.5 14-18 3 96 95 (A1Cla)- (FeCla)a 62-95 0.00455 0. 8 10-25 97 66. 4

1 Usually finished at lower pressures.

5 In stages (a) time of addition (0.5 to 1 hr.), (b) holding (1 hr.),(0) finishing (0.5 hr.). Times given in parentheses are those usuallyemployed 3 In the actual run, some olefin was present; this conversionis calculated on the basis of tertiary alkyl chloride concentration.

butane :(1-1-2) were charged to the dropping funnel. The contents of thefunnel were added over a 2 hour period, while the flask was maintainedat 7-8 C. and 400 mm. pressure. Thereafter, the contents were held at1.5 hours at -the same temperature and pressure. After 3.5 hours, thepressure was reduced to 100 mm. Hg and held for 15 minutes. The reactionwas terminated by pouring Referring particularly to Table I, it shouldbe noted that the selectivity of the alkylation reaction has been themixture over an-ice-salt mixture and worked up as 75 a considerablylowerselectivity was encountered, it is to obtained by a suitableselection of reaction conditions.

be noted that'a higher 'purity'product could hav'e'bee'n catalyst wasemployed; the

For example, Example 7 showed a'selectivity in some boiling ranges aslow as 86%. These compounds c an be separated by dist'illationfor therecovery or thefhigh purity product or conditions similar to those shownin Example 12 could be employed for highselectivity-(Le,

the pressure could be reduced to 40 mm.). Similarly in Example 11," thepressure/could be reduced for mi km shown below by structural formula,together with the vis- V J V use of the catalyst and proeedure ofExample 13 raises the selectivity to 95%.

Thus it is seen that the present invention relatesto monoanddi-t-alkylbenzeneshaying widely vary-ing carbon numbersin'theialkylgroup;"r I

The compounds produced by alkylation of benzene are cosity thereof wheresuch measurement is available. The

viscosity in those instances is comparedf to'theviscosity of a. normalalkyl benzene;

:irxsm'ipsmummu FoRMULAs 7 I Monoalkyl benzenes, I

V, V So a; V 7 i vii. (is. at'100 F.-

I V p J Alkyl T T0 1 Example Number 1 R -Rr-Rycarbons eerbone t-Alkyln-Alky ...-.;;-......-V......,V;M I. 02H; 7 M 2 2-2 V13'.-------.....-l-:

H zHl Q V V 63H; '7 I 1-1-1 1o I -16 3.73 r

14-9 r 12 18' 1.9' L2 1444* 17' r 11 8.4: M42 x 17 2a'.. 84 24-8 12 '1s-5.3

9 1 10] 7 2&- 21 .--..V.1..,.,--.. ,V..7 I 54-10 17 ea V I Dlallrylbenzenes. 7V V 7 an. 14 2 20 is g "22 1- 1-12 V '-C12Hzs V (22H, 1-1-4ill. 1 17 7; 2-2-2, V c zfisj 9 Example 15 Alkylation of naphthalenewith 3-chloro-3-ethylpentane (2-2-2) using cyclohexane solvent. Theflask was charged with 100 g. of cyclohexane solvent, 25.6 mols ofnaphthalene, and 1.6 g. of FeCl;; (anhydrous). The dropping funnel wascharged with 13.5 g. of the (2-2-2) chloride. The addition was carriedout over a period of 0.3 hour, and to the flask which was maintained at20 C. and 65 mm. Hg. The reaction was hold for an additional 3 hoursunder the same conditions, and then for a half-hour at 20-30 mm. Hg. Theproduct was worked up and found to contain no measurable benzylichydrogen (a hydrogen atom alpha to the aromatic ring). Thus, by reducingthe pressure and using cyclohexane as a boiling liquid, selectivealkylation was accomplished.

The product had the structural formula:

Example 16 Alkylation of alpha methyl naphthalene with 3-chloro-3-ethylpentane (2-2-2) using cyclohexane solvent. A run similar toExample 15 was made using 40 g. of cyclohexane, 28.4 g. of alpha methylnaphthalene and 1.6 g. of FeCl (anhydrous) in the flask, with 13.5 g. of3- chloro-3-ethylpentane (2-2-2) in the dropping funnel. The additionwas carried out over 0.13 hour, the flask being maintained at 22 C. and65 mm. Hg. The reaction was held under those conditions for anadditional 3 hours and then for 0.5 hour at 20-30 mm. Hg. After a workupof the product, the NMR analysis showed 65.2% alkylation based on thetertiary chloride. Ninety percent of the product was3-ethyl-3-naphthylpentane and nearly 3-methyl-3-naphthylpentane withpossible traces of 2-methyl-2-naphthylpentane. It is to be noted thatalthough the tertiary alkyl group isomen'zed, the product was still atertiary alkyl. No measurable quantity of benzylic hydrogen was found inthe alkylated product. The maximum HCl concentration during alkylationwas calculated to be 0.00034 mol fraction.

The primary product has the structural formula:

gi t.

ent process.

Example 17 Alkylation of t-butylbenzene with3-chloro-3-methylpentadecane (2-1-12) in the presence of triethylamine.Thefiask was charged with 114 g. of -tbutylbenzene, 24.3 g. of anhydrousiron chloride, and 8.6 g. of triethylamine. The dropping funnel wascharged with 14 g. of t-butylbenzene and 221 g. of3-chloro-3-methylpentadecane (2-1-12). The addition was carried out fora total of 1.5 hours, while the flask was maintained at a temperature of12-36 C. and 40 mm. Hg. The reaction was held under those conditions foranadditional hour and then the pressure was reduced to about 15 mm. Hgand held for about 0.5 hour. The product was worked up and found torepresent a 24% molar yield based on the tertiary chloride. Only tracesof benzylic hydrogen were discovered by NMR analysis, indicating thattertiary alkylation without isomerization to nontertiary forms had beenobtained. It was noted that considerable interchange of alkyl groups hadtaken place, the highest boiling fractions 10 containing large amountsof di(3-methylpentadecyl)benzene:

C Ha C Ha Cribs-( JC12HZ5 32 's h s Example 18 The following examplesare directed to alkyl benzenes having one or two alkyl substituents. Thealkyl substituents were obtained by dimerizing a-olefins and thenreacting the dimerization product with HCl. The a-olefins employed wereC -C (even-numbered), in admixture or alone.

The resultant t-alkyl chlorides were reacted with benzene, using FeCl asa catalyst and employing the techniques more particularly described incopending applica tion Ser. No. 102,921, Selective Tertiary Alkylationof Aromatic Hydrocarbons by I. K. Boggs and filed on an even dateherewith. After completion of the alkylation reaction, the products wereseparated by distillation.

The following dimerization products were obtained from an admixture of CC C and C a-olefins:

From these olefins, the corresponding t-alkyl chlorides were obtained byhydrochlorination.

The admixture of alkyl chlorides was reacted with boiling benzene in thepresence of FeCl catalyst and under a vacuum to obtain a mixed t-alkylbenzene product. During alkylation, some desirable rearrangement bymethyl shift may occur; e.g., from the halide, the

t-alkyl aromatic structures may also be obtained as well as the expectedt-alkylated aromatic. The product exhibited an alkyl-substituent carbonnumber distribution as follows:

Mol percent Nil QC 1.0 QC 15.1 QC 32.6 0C 32.3 QC 19.0

fifi The symbol 0 indicates benzene nucleus; hydrogen quantities areomitted.

ethylene type C isoolefins and the corresponding tertiary alkylchlorides. The olefin mixturewas made up of 34 mol percent of10-methyleic0sene-9, 51 mol percent of i i t the alkylating' mixture to293g.v of benzene and g; of

7 aluminum'chloride over a period of 60' minutes whileIO-methyleicosene-IO, and 15 mol percentof Z-nonyldodecene-l:

CH; CH3 cingon=ir-cmn=i overpower- 0in -methyleleosene-9IO-methyleicosene-IO o ibf V C=CH1- mHn V 2-nonyldodecene-1 V Thetertiary alkyl chloride is derivedtrom the mixture; of three olefins,and has the structure:

' on, 1 QoH1o- 1eHn V a V V I p 1'q-ehloro ',"1o-m' k I J M I .7'Aneumixtureorizss gr'of theolefin niixturegand 258g. of the alkylchloride'plus 293 g. of benzene was added to 293 g. of benzene and 5 g.of A101 over a period of 60 minutes while stirring the liquid reactionmass. The temperature varied from 5 C. to C. during the reaction period.A vacuum was maintained, the pressure during the reaction being about 60mm. Hg absolute. After termination of the reaction the product wasrecovered and found to have the following analysis:

The productxwas compounded to produce an aviation hydraulic fluid havingthe characteristics shown in Table Viscosity, cs. at 100 F Viscosity indax 97 Pour point, F -60 Flash point, F 470 Oxidation/corrosionstability 0 Pass Thermal/corrosion stabi1ity.. Pass I Blended asfollows: Synthetic oil, 98 wt. percent; Trierasyl phosphate, I V

1 wt. percent; Antioxidant (ethyl 702), '1 wt. percent.

b The finished blended oil may also contain VI improver and pourdepressants as desired.

a As determined by MILH27601A.

Example 20 Benzene was alkylated with amixture of internal C isoolefinsand the corresponding tertiary alkyl chloride- The olefin mixture wasmade up of 32 volume percent of ylhexadecene-G: on,

i-6-methylhexadecene-5 and 68 volume percent of 6-meth- The tertiaryalkyl chloride isderived from/both of theabove-mentioned olefins and hasthe structure:

An admixture of 139 g. of the olefin mixture, 274' g. of the alkylchloride," and 293 g. of benzene was added as stirring the liquidreaction mass. The temperature varied 1 from 5 C. to 15 C;. during thereaction period; A vacuutn was maintained; the pressure during thereaction be-' ingabout 60 mm. Hg. absolute. After termination ofrthereaction, the product was recovered and found to have t the followinganalysis; 7 a

The product was compounded to produce an aviation hydraulic fluid havingthe characteristicsshown inTable. IY

below;

I TABLE rvrnmrronnYnnnurzro rnurn b Sinners in f V 7 CH3 CH3 s ur-I JCniHn c a m -rCli CmH'zr,

(Example 20) (Examplem) Viscosity, 0S. at F 13.04 18. 99 Viscosityindex. 37 97 Pour point, F- 55 60 Flash'pointfi F 420 470Oxidation/corrosi stability Pass Pass Thermal/corrosion stability PassPass I Blended as follows: Synthetic oil, 98 wt.percentrTricresylphosphate, 1 wt. percent; Antioxidant (Ethyl 702), 1wt. percent;

b The finished blended oil may also contain VI improver and pourdepressants as desired.

As determined by MIL-H-27601A.

We claim: 7

1. A: composition useful as a lubricant and consisting essentially of anadmixture of monosubstituted tertiary alkylbenzenes in the approximateproportions;

Mol percent C H t-alkyl benzene 1.0 C13H37 benzene C H t-alkyl benzene32:6 7 C H t-alkyl benzene 32.3 C H t-alkyl benzene u- 19.0

chlorinated internal olefin, under conditions includan eifective amountof a Friedel-Crafts catalyst, V

a temperature from -l0 C. to +30 0.,

a pressure from 20 to mm. Hg absolute,

and in the presence of an ebullient liquid, said conditions beingcorrelated so as to remove HCl from the reaction zone at a ratesutficient to minimize the formation of undesirable secondary alkylisomers.

3. A composition consisting essentially of one or more compounds having.the formula:

13 14 wherein: 3,115,530 12/1963 Cohen 260671 B A is benzene ornaphthalene, 3,234,297 2/1966 Cohen 260671 B R, is hydrogen or atertiary alkyl group, 3,238,249 3/ 1966 Mirviss et al. 260-671 B R ismethyl, 3,403,195 9/1968 Patton et a1 260-671 P R is a C or a C alkylgroup, and 5 OTHER REFERENCES R is a C to C alkyl group.

4. A composition according to claim 3 wherein R is C alkyl and R is Calkyl.

5. A composition according to claim 3 wherein R is C8 alkyl and R2 is Cm1 1 10 Pines et aL: JACS, vol. 71, November 1949, pp.

6. A composition according to claim 3 wherein R is C9 alkyl and R2 is C9alkyL Pines et al.: JACS, vol. 75, February 1953, pp. 937-9.

References Cited Eglofi: Physical Constants of Hydrocarbons, vol. 3,1946, pp. 144, 145, 152-5, 159, 165, 169-172, 174, 176, 177

CURTIS R. DAVIS,- Primary Examiner UNITED STATES PATENTS 15 CL 3,115,46512/1963 Orloff et a1. 252 49.9 3,357,920 12/1967 Nacson 252-499 252 260668 671 671 671 P 2,796,429 6/1957 Kreps et a1 260-671 B

